Co-polymers from aryl-substituted butenyl alcohols, ethers, and esters and a conjugated diene, compositions containing same, and method of making



James N. Short, Borger, Carl A.

United States Patent CO-POLYMERS FROM ARYL-SUBSTITUTED BU- TENYL ALCOHOLS, ETHERS, AND ESTERS AND A CONJUGATED.DIENE, COMPOSITIONS CON- TAINING SAME, AND METHOD OF MAKING Uraneck, Phillips, and Alvin C. Rothlisberger, Borger, Tex., assignors to Phillips Petroleum Company, a corporation of Delaware No Drawing. Application November 23, 1953 Serial No. 393,924

19 Claims. (Cl. 260-415) This invention relates to a new class of materials suitable for use in the production of homopolymers of these materials as well as copolymers using monomers copolymerizable therewith. In a further aspect, this invention relates to homopolymers of aryl-substituted butenyl alcohols, ethers, and esters. In a further aspect, this invention relates to copolymers of these alcohols, ethers, and esters with comonomers polymerizable therewith. In a further aspect this invention relates to new polymeric materials, these materials ranging from liquids to elastomers to hard resins.

Each of the following objects is obtained by at least one of the aspects of this invention.

An object of this invention is to provide polymers prepared using a new class of polymerizable materials. A further object of this invention is to prepare polymers from aryl-substituted butenyl alcohols, ethers and esters. A further object of this invention is to provide polymeric materials prepared from aryl-substituted butenyl alcohols, ethers, and esters and materials copolymerizable therewith. A further object of this invention is to provide a variety of polymeric products ranging from liquids to elastomers to resins. A further object of this invention is to provide rubbery materials having excellent green tensile properties. A further object of this invention is to provide binders for solid materials.

Other objects and advantages of this invention will be apparent to one skilled in the art upon reading the accompanying disclosure.

We have found a new class of materials which are valuable for the production of new polymeric materials, this term including copolymers as well as homopolymers. The monomeric materials from which these new polymers are prepared can be represented by the formula where R is an aryl radical, A and 2,834,747 Patented May 13, 1958 2 where R is an aromatic radical or a saturated aliphatic radical. In this structural formula R and R may be substituted or unsubstituted. Substituents on these radicals can be halogen, such as fluorine, chlorine, bromine, and iodine, hydroxy, cyano, keto, carboxy, alkyl, aryl, aralkyl, alkoxy, aryloxy, amino and. substituted amino groups, the only limitation upon these groups being that they not be so large or numerous as to cause steric hindrance which interferes with the polymerization. Generally R should contain not more than 12 carbon atoms and the number of carbon atoms in Xshould not exceed 18. A further group of monomers applicable for use in the present invention includes compounds having the structural formula set forth above where X is bromo-4-methylphenyl)- 4-hydroxy-lbutene, 2 l-naphthyl)-4-acetoxy-l-butene, 2-(2-methoxyphenyl)-4-hydroxyl-butene, 2-phenyl-4-capryloxy-l-butene, 2-phenyl-4-propionoxy l butene, 2-(3-methylphenyl)-4-valeroxy-1-butene, 2-(2,4,6-trimethylphenyl)-4-hydroXy-1-butene, 2-(2- methyl 4,6 -diethylphenyl) 4-acetoxy-1butene, 2-[2-(4- methyl)naphthyl] -4- acetoxy -1- butene, 2-phenyl-4-methoxy-lbutene, 2 phenyl-4-monochloropropoxy-l-butene, 2-phenyl-4-isobutoxy-l-butene, 2-phenyl-4-n-nonyloxy-lbutene, 2 phenyl 3 methyl 4 ethyl-5,8,1l-trioxa, 2- hydroxy-l-tridecene, 2-phenyl-4-benzoxy-l-butene, 2- phenyl-4-(3 methoxybenzoxy)-lbutene, 2-phenyl-4-(2- aminoethoxy) l-butene, 2-phenyl-4- 2-hydroxythoxy) -1- butene, 2-phenyl-4-lauryloxy-l-butene, 2-phenyl-4-stearyloxy-l-butene, 2-phenyl-4-acryloxy-l-butene, 2-phenyl-4- crotonoxyl-butene, 2-phenyl-4-(Z-cyanoethoxy) -1-butene, 2 phenyl 4 -(2ketobutoxy)- 1- butene, 2 phenyl-4-(3- carboxypropoxy)-l-butene, 2-phenyl-3-(acetoxymethyl) l-pentene, 2-phenyl-3-methyl-4-carpyloxy-l-pentene, 2- phenyl 4 (N,N-dimethylaminoacetoxy)-l-butene, 2(3- fluorophenyl)-4-(N,N-diethylaminoacetoxy)-1-butene, 2- (2 iodophenyl)-4-(n methyl-N-propylarninoacetoxy)-1- butene, 2 -(4-N,N-dimethylaminophenyl) 4 hydroxy-1- hexene, 2-phenyl-3-methyl-4-(2-N,N-di-tert-butylaminoethoxy) -lbutene, and 2-pheny1-5-oXa-8,l1,14-azo-l6- amino-l-hexadecene. The preferred species of these materials are 2-phenyl-4-acetoxyl-butene, 2-phenyl-4-hydroxy-l-butene. A method which can be employed for the production of many of these monomers is that described by alcohol or its derivative is employed per 3 Price, Benton, and Schmidle, J. Am. Chem, Soc.'7l, 2860 (1949). For example, alpha-methylstyrene is reacted with paraformaidehyde in the presence of acetic acid and then with acetic anhydride to give 2-phenyi-4-acetoxy-1- butene. Hydrolysis of this ester yields the hydroxy compound, i. e., 2-phenyl-4-hydroxy-l-butene. Ethers and the higher esters can be prepared by reacting the hydroxy compound with the desired alcohol, or acid, to give additional compounds such as those described above. Saturated and unsaturated aliphatic monocarboxylic acids, and monocarboxylic aromatic acids can be used. Acid anhydrides can be substituted for the acids.

Another method in which the esters can be prepared comprises the use of an acid chloride and a hydrogen chloride acceptor. For example, the caprylate can be prepared by reacting caprylyl chloride with 2-phenyl-4- hydroxy-l-butene dissolved in pyridine, as well as by direct esterification with caprylic acid. Finally, ester interchange can be used for their production.

These monomeric materials can be polymerized alone or with other copolymerizable compounds, i. e., compounds containing an active vinylidene group, i. e., CH =C Representative copolymerizable compounds include conjugated dienes such as 1,3-butadiene, isoprene, chloroprene, 2,3-dimethyl-l,3-butadiene, 1,3-pentadiene, and those dienes capable of coreacting sufiiciently to give significant monomer reactive ratios as defined by Mayo and Walling, Chem. Rev. 46, 196 (1950); and monoolefins which are copolymerizable with alpha-methylstyrene such as nuclear derivatives of alpha-methylstyrene, isobutylene, styrene, maleic anhydride, unsaturated ethers or esters, vinylidene chloride, acrylonitrile, methyl vinyl ketone, acrylic esters, methacrylic esters, and other monoolefins capable of coreacting sufiiciently to give significant monomer reactivity ratios. Vinylpyridines, such as 2- methyl-S-vinylpyridine are also applicable.

In the preparation of these polymers, the amount of aryl-substituted buetenyl alcohol, ether, or ester canbe varied from 0.1 to 100 parts of the monomeric material. Generally at least 1 part of the aryl-substituted butenyl hundred parts of the monomeric material, it being understood that mixtures of difierent aryl-substituted butenyl alcohols or their derivatives can be employed as well as mixtures of these compounds with various other monomeric materials.

A particularly valuable group of materials which can be prepared according to this invention are those in which a copolymer is prepared using 2.-phenyl-4-hydroxy-1- butene and the esters thereof and a conjugated diene such as those mentioned above. When copolymerized using from 0.5 to 99.5, preferably from to 60 parts of the alcohol per hundred parts of monomers, the resulting polymers are rubbery in nature. The copolymers of the alcohols described above have unexpectedly high green tensile values, the green tensile being the tensile of the material after-all of the rubber compounding in- I gredients have been added, but before the composition has been cured. Rubber having good green tensile properties is necessary where considerable working takes place before the rubber is cured. An example of such an application is the coating of wire with a rubbery material. In such an instance the wire is coated with considerable speed and the coating is subjected to large stresses. If a rubber without good green tensile strength is used thin spots will appear in the insulation. The manufacture of gaskets is another field in which the rubbery material is subjected to stress before curing.

Furthermore, rubber with good green tensile properties will produce a better ultimate product for all applications, although it is not so important in many of these, because the carbon black and other ingredients used'in rubber processing have a marked ability in increasing the tensile properties of the rubber following cure. They can be reinforced with various pigments or dyes.

The materials of this invention are also useful as casting resins, potting compounds, and as binders for solid materials. Homopolymers of the aryl-substituted butenyl alcohols are particularly valuable as plastics coating resins, coating compositions and the like. Filaments having valuable properties can be formed from the polymers of this invention.

The monomeric materials herein described can undergo additional polymerization by any of the methods known to the art such as mass or emulsion polymerization, although emulsion polymerization is to be preferred. Furthermore, they can undergo polymerization by a free radical mechanism, such as occurs in thermal or photopolymerization, or polymerization initiated by peroxides, persultates, hydroperoxides, azo compounds, and the like, or by ionic mechanism such as occurs in acidor basecatalyzed polymerization initiated by sulfuric acid, boron trifluoride, aluminum chloride, sodium, sodium amide, sodium alkyls, etc.

Depending upon the type of polymerization employed and the recipe used, the temperature of polymerization can vary over a very broad range. For emulsion polymerization, the temperature is generally in the range between 40 and C. When Friedel-Cratts type catalysts are employed, the polymerization temperature is sometimes as low as l00 C. or even lower. In instances where catalysts of the alkali'metal type are chosen, temperatures in the range between 20 and 110 C. can be employed.

Rubbery materials having excellent properties are readily prepared by the copolymerization of conjugated dienes with the monomers of this invention. For example, the copolymers of 2-phenyl-4-hydroxy-1-butene with 1,3-butadiene possess improved green strength, i. e., the compounded but uncured rubbers have exceptionally high tensile strength. When the rubbers are evaluated as tread stocks for tires, they show a good balance of properties and both unaged and aged samples show superiority in abrasion resistance to butadiene/a-methylstyrene and butadiene/ styrene rubbers prepared at 41 F., and also to natural rubber. These rubbers also show superiority in low temperature properties.) They are well suited for carcass stock applications, particularly the butadiene/2-phenyl-4-hydroxy-l-butene copolymer which has improved hot tensile strength. When compounded in a silica recipe, the butadiene/Z-phenyI-4 acetoXy-lbutene copolymer possessed unusually high but tensile strength in comparison to butadiene/ styrene and natural rubbers. Copolymers of these alcohols are easily proces'sable.

Example I Copolymers of butadiene with 2-phenyl-4-acetoxy-lbutene an'd 2-phenyl-4-hydr'oxy-l-butene were prepared by emulsion polymerization at 41 F. in accordance with the following recipes:

1 Potassium Synthetic Rubber Division soap. Sodium salt of condensed alkyl aryl sulionic acid.

Two runs were made for the preparation of /25 butadiene/a-methylstyrene copolymers at 41 F. in accordance with the following recipe:

Parts by weight 1 Rosin soap, K salt. Neutral sodium salt of a condensed aryl sulfonic acid.

Results of the four runs were as follows:

with natural rubber. The following basic recipes were employed:

Parts by Weight Synthetic Natural Rubber Elastomer 100 100 Carbon black (Philblack O) 50 50 Zinc oxide 3 4 Stearie acid 2 3 Sulfur 1. 75 2 Flexamine l 1 1 Circosol-Paraflux blend 5 Santocure 3 4 variable 0.5 Pine tar. 3

1 A physical mixture containing 65 percent of a complex diarylamineletone reaction product and percent of N,N-dlphenyl-p-phenyleneammo.

2 /50 blend of Circosol-2XH and Paraflux CiroOsol-ZXH: a petroleum 2O hydrocarbon softener, containing hydrocarbons of high molecular weight,

in the form of a heavy, viscous, transparent, pale green, odorless liquid Conversion of low volatility; sp. gr. 0.940; Saybolt Universal viscosity at 100 F., Mooney about 2,000 seconds. Paraflux: saturated polymerized hydrocarbon. copolymer value 3 N-cycloheXyl-2-benzothiazolesulfenamide.

Time Pep 4 Except the butadiene/styrcne copolymer, 1.0 part stearic acid. Hour cent 4 Butadiene/2-phenyl-4-acetoxy-1-butene, 0.8 part; butadiene/2-phenyl- 4-hydroxy-1-butene, 0.7 part; butadiene/a-methylstyrene, 0.9 part;

. butadiene/styrene, 1.0 part. Butadiene/2-phenyl-4-acetoxy-l-butene... 14. 8 66 59 3ugagieneN-phenlyl-i-hydroxy-l-butene 19. 9 en n Bfi, i$ g n 62 The stocks were milled, cured 30 minutes at 307 F. and physical propertles determined. The results were as follows:

F. Freeze Point Oom- Comp. pound- Oonver- 200 F. Resili- Flex Shore Abra- Set, Raw ed Elastomer sion, 300% Elon- Tensile, A'l. F. ence, Life, Hardsion 2Hrs. at Geh- ML-4 MS 1% percent Mod- Tensile, gation, p.s. 1. percent M I new Loss, g. 212 F. man, T-R, at

ulus, p. s. 1. percent 0. 0. 212 F; p. s.i.

Butadiene/2-phenyl- 4acetoxy-1-butene- 66 1, 415 3, 300 530 1, 520 67. 9 65. 1 11. 2 54 4. 80 18. 9 71 -63 59 44 Butadiene/2-phenyl- 4-hydroxy-l-butene 62 1, 490 3, 440 490 1, 580 65. 5 65. 9 16. 3 54. 5 3. 48 15. 3 64 -58 71 56. 5 Butadiene/a-methylstyrene 72 1, 690 3, 820 510 1, 800 64. 2 67. 0 29. 1 57. 5 5. 89 17. 0 -56 -51 75 53 Butadiene/a-methylstyrene 62 1, 550 3, 900 540 l, 820 67. 2 67. 2 35. 5 57 6. 26 17. 0 59 -53 65 49 Butadlcne/Styrene- 1, 480 3, 450 535 1, 830 67. 6 63. 1 l7. 2 53. 5 5. 48 18. 6 55 47 48 38 Natural rubber 1, 625 3, 200 480 2, 660 47. 6 69. 2 2 8. 8% 58 8. 96 19.0 61 59 31. 5

OVEN AGED 24 HOURS AT 212 F.

Butadiene/2-phenyl- 4-acetoxy-1-butene- 66 2, 775 3, 060 320 60. 2 69. 7 7. 3 63 3. 57 Butadienel2-phenyl- 4-hydroxy-1-butene 62 3, 310 280 55. 1 71. 4 4. 9 62. 5 But-adiene/a-methylstyrene 72 2, 870 3, 125 320 54. l 70. 2 17 2 62 Butadiene/a-rnethylstyrene 62 2, 685 3, 485 370 55. 1 71. 1 10. 5 62 Butadiene/styrene 2, 715 3, 460 370 56.1 68. 7 11. 5 62 Natural rubber 1, 875 2, 325 43. 3 74. 4 30. 5% 61. 5

1 Thousands of fiexures to failure.

4 Percent broken in 50,000 flexures.

The four elastomers prepared as described above were evaluated in a tread formulation together with a sample of a 41 F. 75/25 butadiene/styrene elastomer and also 75 These data show that the butadiene/2-phenyl-4-acetoxyl-butene and butadiene/2-phenyl-4-hydroxy-l-butene copolymers have a good balance of properties and both unaged and aged samples show superiority in abrasion stance to the other elastomers tested. The new polymers also show superiority in low temperature properties resi These data show that the butadiene/2-phenyl-4-acetoxy-l-butene and bntadiene/2-pheny1-4-hydroxy-l-butene as evidenced by the freezing point. copolymers have a good balance of properties and that the .butadiene/2-phenyl-4-hydroxy-l-butene copolymer Example II 5 has greater tensile strength in both nnaged and-aged samples than the other synthetic elastomers tested. It The 'elastomers i h r evaluated in the tread also has superior tack to the other synthetic elastomers. formulation described in Example I were also evaluated in a carcass formulation.

below.

Example III Two butadiene/2-phenyl-4-acetoxy-l-buteue and two Compounded Raw at 212 F.

Meter Tack MSBi ML-4 Com- Set, percent Shore pression Hardness Flex Life,-

Resilience, percent butadiene/aemethylstyrene copolymers were prepared by Butadiene/ Styrene p. B- i.

sso

Elon Tensile, AT F.

a-methylstyrene percent nsi gation, p. s. i.

OVEN AGED 24 HOURS AT 212 F.

Parts by Weight butane 0535000574. 02 .1 1 QII-OZO 300% Mod- Te ulus. p. s. i.

The basic recipes-are shown Butadienel Butadiene/ Bntadiene/ 2-phenyl-4- 2-pheny1-4- acetoxy-lhydroxy-ibutene w535000586 2 s 1 1 211520flw Conversion, percent Elastomer- Carbon black (Philblack O)- Zinc oxide Sailor.--"

Stenrie aeid I Polymerized trimethyldihydroqulnoline.

1 As in Example I.

I Hydrogenated rosin.

I Reaction product of butyraidehyde and butylidene aniline.

The stocks were milled, cured. 30 minutes at 307 F., and physical properties determined. The following results were obtained Elastomer butenm Bntadiene/Z phenyl 4 hydroxy 1- Butadiene/2 phenyl 4 acetoxy i- 1 Percent brokentn 50,000flexures.

Butadienel). phenyl 4 acetoxy l- Butadiene/2 phenyl 4 hydroxy 1- Natura1rubber.

9 t t emulsion polymerization at 41 F. in accordance with the following recipes:

Parts by Weight Recipe A Dresinate 214 K-SRD soap Triton 12-100 Daxad 11 4 N8sPO4.12HzO KC] 0. tort-On mercaptan variable variable Oumene hydroperoxide- 0. 125 0. 125 K4P207 0. 22 0. 22 FBSO4.7HQO 0. 20 0. 20

l Rosin soap, K salt.

I Potassium Synthetic Rubber Division soap.

3 Neutral sodium salt of a condensed aryl sulionic acid. 1 Sodium salt of condensed alkyl aryl sulfonic acid.

The following table gives the amount of mercaptan employed in each case and the results of the runs.

Conversion ten-C12 Mnnnny Second Monomer Mercap- ML-4 tan, Part Tim Per- Hours cent 2-Pheny1-4-acetoxy-l-butene O. 15 14. 1 57 69 2-Phenyl-4-acetoxy-l-buten 0. 14. 1 58 52 a-Methylstyrene 0. 15 13. 7 61 64 a-Methylstyrene 0. 20 13. 7 60 44 A blend of approximately equal parts of the two butadiene/2-phenyl-4-acetoxy-l-butene copolyrners was prepared. Similarly a 50/50 blend of the two butadiene/amethylstyrene copolyrners was prepared. These blends were evaluated in a silica loaded stock together with the butadiene/ styrene copolymer described in Example I and also with natural rubber. The following basic compounding recipes were employed:

Parts by Weight Synthetic Natural Fla. fmnm- 100 1 Silica 70 Zinc mrirla 3 S ur 1. 75

Stearic acid 1 2.0 and 1.0

Flexamine 1 1 Circosol-Parafiux blend 1 5 Santocure 9 2 1. 2 Diphenylguanidine 0. 4 Pine tar 3 1 One part stearic acid for the butadiene/styreue copolymer. 1 I As in Example I.

The stocks were milled, cured 45 minutes at 307 F.,

Recipe B Q and physical properties determined. The following results were obtained:

- 212? F. 300%, Tensile, Elonga- Tensile Modulus, p. s. i. tion, 5

p. s. i. 7 percent Butadiene 2 phenyl 4 acetoxy-l-butene 2, 000 3, 470 2, 070 Butadiene/a-methylstyrene. 2, 070 2, 900 410 1, Butadiene/styrene 1, 690 1, 950 360 910 Natural rubber 870 1, 910 500 790 These data show the superiority of the bu'tadiene/Z- phenyl-4-acetoxy-l-butene copolyrners over the other elastomers in both 80 F. and 212 F. tensile strength.-

These data illustrate an unexpected property of the polymers of this invention, which is that silica exhibits a considerable reinforcing action. In natural rubber, silica acts as a filler with negligible reinforcing properties.

Example IV 2-phenyl-4-acetoxy-l-butene was copolymerized with butadiene and isoprene using variable amounts of the monomers. The following 41 F. emulsionpolymerization recipe was employed:

Parts by weight Diene Variable Second monomer Variable 180 K-SRD soap 1 5.0 Daxad 11 1 0.20 KCl 0.50 Tert-C mercaptan 0.20 Tert-butylisopropylbenzene hydroperoxide 0.104 K P O 0.165 FeSO .7H O 0.139

1 A e in Example I.

The following table gives the .ratio of monomers employed in each case and the time-conversion data.

p The following 41 F. emulsion polymerization recipe was employed for the preparation of copolyrners of butadiene with 2-phenyl-4-acetoxy-l-butene and 2-phenyl-4- hydroxy-l-butene and terpolymers of these materials With styrene:

Parts by weight Monomers 100 Water 180 K-SRD soap 1 5 .0 Daxad 11 1 0.20 KCl 0.50 Tert-C mercaptan 0.20 Tert-butyliospropylbenzene hydroperoxide 0.104 K P 0 0.165 FeSO .7H O 0.139

1 As in Example I.

aeeom'r The 'butadiene/2-phenyl-4-acetoxy-l-butene and butadiene/2-phenyl-4-hydroxy-l-butene elastomers described in Example I were analyzed to determine the amount of combined 2-phenyl-4-acetoxy-l-butene and 2-phenyl-4- hydroxy-l-buteue, respectively, in the copolymers. The results were as follows:

7 Weight percent Combined 2-phenyl-4-acetoxy-l-butene in copolymer 19 Combined 2-phenyl-4-hydroxy-l-butene in copolymer 15.7

Example VII The following recipe was employed for the production of 50/50 butadiene/2-phenyl-4-acetoxy-l-butene copoly- :mers by emulsion polymerization at 41 F. using difierent oxidants:

Parts by weight Butadiene 50 2-.phenyl-4-acetoxy-l-butene 50 Water 180 K-SRD soap 1 5 Daxad 11 0.20 Tort-C mercaptan 0.20 K P 0.22 F6804-7H20 KCl 0.50 Oxidant Variable 1 As in Example I. The following table gives the oxidant employed in each case and the results obtained:

Oxidant Conversion, Percent Type Parts 3.2 24 118 Hours Hours Hours Cume-ne hydroperoxide 0.125 8. 9 52. 9 67. 3 tort-Butylisopropyl-benzene hydroperoxide 0. 171 19. 8 66. 6 tert-Dodeeyllsopropyl-benzene hydroperoxide 0. 263 21. 9 64. 8 tert-Octadecylisopropyl-benzene hydroperoxide 0. 333 25. 7 42. 7 54.

Example VIII The monomer ratios and results are glven below. anhydride, and a-methylstyrene were removed by vacuum Monomers Conversion, Percent Retractive In- Type Ratio 2.9 5.7 24 70.2 dex Hours Hours Hours Hours Butadiene/2 -pheny1 4 acetoxy-l-butene 75125 34 56 88 '1. 5236 Butadiene/styrenel2-phenyl+ acetoxy-l-butene 75/ l2.5/12.5 45 72 90 93 1. 5292 Butadiene/styrene/ 2- phenyl 4-acetoxy-1-butene 50/25/25 35 54 78 81 1. 5452 Butadiene/Z phenyl 4 hydroxy-l-butene 75/25 10 20 57 76 1. 5259 Butadiene/styrene/Z-phenyl- 4-hydroxy-1-butene 75/12.5/12.5 22 43 78 85 1. 5312 v Butadiene/styrene/2 phenyl -hydroxy-bbutene 50/25/25 13 20 54 70 1. 5472 Example VI d stillation. The residue was distilled to gWeZ-PhenyI-A- acetoxy-l-butene boiling at 95-102 C. at a pressure of 0.3-0.7 mm. of Hg. i

Example IX The following run demonstrates the preparation of 2- phenyl-4-hydroxy-1-butene:

A solution containing 700 grams KOH, 700 cc. water, and 1000 cc. isopropyl alcohol was prepared, cooled, and charged to a reactor provided with a stirrer, reflux condenser, and means for adding the material tobe hydrolyzed. Seven moles (1330 acetoxy-l-butene was added, with stirring, to the KOH solution. The mixture was then refluxed four hours, cooled, the upper alcohol layer separated and washed twice with .two liters of water, and then dried over anhydrous potassium carbonate. Upon distillation the 2- phenyl-4-hydroxy-l-butene was obtained which boiled at 63 C. at a pressure of 0.15 mm. of Hg or 73'" C. at a pressure of 0.3 mm. of Hg.

Example X 2-phenyl-4-capryloxy-l-butene was synthesized from 2- phenyl-4-hydroxy-l-butene and caprylyl chloride andthe product copolymerized at 41 F. with butadiene in accordance with the following recipe:

Parts by weight Example XI Butadiene was copolyrnerized with 2-phenyl-4-capryloxy-l-butene using the recipe given in Example X except that a 50/50 monomer ratio was employed. A' conversion of 76 percent was obtained in 10.5 hours.

Example XII Butadiene (75 parts) was copolymerizcd with Z-phenyl- 4-monochloroacetoxy-1-butene (25 parts) in accordance with the recipe given in Example X. At 5.25 hours a booster of 0.41 millimole of tert-butylisopropylbenzene hydroperoxide and 0.36 millimole of ferrous pyrophosphate was added. A conversion of 18 percent was obtained in 6.25 hours.

Example XIII Butadiene/styrene, butadiene/alpha-rnethylstyrene, butadiene/2-phenyl-4-acetoxy-1-butenc, and butadiene/Z- phenyl-4-hydroxy-l-butene copolymers were prepared by grams) of 2-pheayl-.4-

the following recipes:

F. in accordance with lation using the following recipes:

The reactions were shortstopped' with 0.3 percent by weight (0.2 percent for the butadiene/2-phenyl-4-hydroxy-l-butene copolymer), based on the monomers charged, of di-tert-butylhydroquinone and 2 percent by weight of phenyl-beta-naphthylamine, based on the poly- Parts by Weight 5 Parts by Weight a ig 50 50 50 Butadiene/ Butadiene/ Butadienel gfi fi g gg Butadiene/ a-methyL 2-phenyl-4- 2-phenyl-4- 2-phenyl-4-acetoxy-l-butene. Styrene Styrene fifigzg iggg; 2-phenyl-4-hydroxy-l-butene 3 11 resina e Fewacidsoapfl il tfgrf earzrtn Pmassium mate black 50 50 o 50 Potassium myristate Zmc oxide 3 3 3 3 Triton R'loo 3 Stearlc acid 2 2 2 2 D e 0 50 Flexamine I: 1 1 1' 1 0120 6.30 i o. 075 15 g g fi 5 5 5 V 5 8 1. 75 1. 75 1. 75 1. 75 0 171 171 Santocure 0. 95 1. 0. s0 0. 70 -sas sa: 8-23 0. 50 0 50 As in Example I.

20 o 1 ROSm soap, potassium salt. The stocks were milled, cured minutes at 307 F. 3 Potassium Synthetic Rubber Division soap. d h 1 Neutral sodium salt of a condensed aryl sulfonic acid. an P yslcal Propel-mes determlned- The results were -5 Sodium salt of condensed alkyl eryl sulfonic acid. f ll 212 F. 80 F. Com- 200 F. Resll- Exan F. Freeze Compres- Tenience, Flex Shore swelled, tracted, Tear bounded Description sion 300% Ten- Elongasile, AT, F. per- Life, Hardperper- Resist- MS 1% Set, Modusile, tion, p. s. i. cent M ness cent cent ancc, Gehat perlus, p. s. l. per- 1b./1I1. T-R, 0. man, 212 F. cent p. s. 1. cent 0.

gugagenestyrenm 16. 6 1, 860 3, 670 615 2, 070 67. 2 58. 8 I 70% 62. 5 146. 1 6. 7 345 22 32 36. 5 u a ene ozmethyl-styrene- 14. 8 2, 160 3, 600 490 2, 230 66. 2 57. 6 I 87. 7% 66 152. 0 6. 9 375 24 -31 38 Butadiene/Z-phenyliacetoxy-lbutene 1B. 6 1, 660 3, 160 530 1, 850 67. 2 58. 7 37. 3 148. 8 10. 0 375 -36 49 31 Butadiene/Z- phenyl-ihydroxy-lbutene 15. 0 1, 950 3, 560 520 2, 160 70. 3 52. 7 51. 2 63 73. 7 l0. 2 335 22 -33 36 OVEN AGED 24 HOURS AT 212 F Butadienelstyrene 2, 600 3, 500 395 58. 5 58. 0 31- 5 6 Butadiene/amethyl-styrene- 2, 800 3, 620 400 60. 2 57. 8 17. 2 71 Butadiene/Z-phenyl- 4-acetoxy-1- butene 2, 440 3, 500 430 60. 2 58. 3 26. 9 65 Butadiene/Z-phenyl- 4-hydroxy-1- butane 3, .500 3, 980 350 61. 5 50. 1 27- 9 0 I Percent broken in 50,000 fiexures. Oven aged properties are minute cure.

Example XIV evaluated in a carcass formulation.

follows The recipes were as mer, was added as the antioxidant. arts yweight Results from the four runs were as follows. Butadienel Butadiene/ Butadiene/ Butadiene/ a-methyl- 2-pheny1-4- 2-phenyl-4- styrene styrene acetoxy-lhydroxy-lbutene butene Conversion Elastomer 100 100 100 100 y Carbon black (Phil- Copolymer Value, black 0) 25 25 25 25 Time, Per- ML-4 Zinc oxide--- 3 3 3 3 Hours cent Stearic acid.... 2 2 2 2 Agerite Resin D 1 1 1 1 5 5 5 5 Butadiene/styrene 10 60 50 2.5 2.5 2. 5 2.5 Butadiene/alpha-methylstyrene 14 62 46 2.5 2. 5 2. 5 2.5 Butadiene/2-phenyl-e-acetoxy-l-butene 11.4 67 40 0.95 1.25 0.80 0.70 Butecliene/Z-phenyl-4-hydroxy-1-butene 46. 8 54. 5 50 0. 19 0.25 0. 16 0. 14

The four elastomers were evaluated in a tread formu- 1 As in Example II.

The stocks were milled, cured 30 minutes at 307 F and physical properties determined. The following results were obtained:

F. ii

212 F. 80 F. 200 F. Gom- Maxi- Resili- Shore Tear Re- Com- Descrlption presmum AT, F. ence, Flex Hardsistance, pounded sion Set, 300% Tensile, Elonga- Tensile, percent Life, M ness MS 1% percent Modulus, p. s. 1. tion, t p. s. i. 1b./in. at 212 F p. S. 1. P9111911 Butadienelstyrene 15. 3 930 3, 700 590 840 36. 6 70. 2 18. 8 50 165 Butadiene/a-methyl-styrene. 13. S 900 3, 820 590 740 37. 1 68. 1 16. 8 52 155 18. 5 Butadiene/Z-phen l e-acetoxyl-butene 1a 4 630 s, 600 660 800 37. 1 e9. 6 i4. 3 46 235 17 Butadiene/2-phen hydroxyl-butene .5 880 4, 230 e00 600 as. 5. e1. 2 27. 2 51 235 20. s

OVEN AGED 24 HOURS AT 212 F.

Butadlene/styrene 1, 500 3,600 500 32. 7 71. 6 7. 9 s4. 5 Butadiene/a-methylstyrene 2, 090 3, 680 460 37. 1 71. 0 4. 5 56 Butadiene/2-phenyl-4-acetoxyl-butene 1, 180 2, 970 500 35. 1 72. 2 4. 8 50 Butadiene/2-phenyl-4-hydroxyl-butene 1, 730. 4, 080 470 37. 1 59. s 7. 7 s5. 5

The compounded stocks were cured minutes at 307 Example XV F. and physical properties determined. The following re- 2 sults were obtained: 2-phenyl-4-lauryloxy-lbutene was prepared by the re- U y d am I action of lauroyl chloride with 2-phenyl-4-hydroxy-lat, want 17 3 butene in pyridine. The product was an amber liquid 86 3 SS 33 14310 which crystallized slightly below room temperature. Re- T 51 i 1 1910 crystallization from ethyl alcohol gave a nearly white 30 f a :5 "'T 360 product. The product had the following properties: afi g c {Fig-"g"; 1040 Refractive index n 1.4948; density 11 0.9441; AT 0 .1 maximum e s 58 5 molar refractivity M 102.05; bromine number 48; purity R r E by saponifioa'tion 100 percent. f q i percen "Z55T1'gf25h55 1 A copolymer of butadiene and 2-phenyl-4rlauryloxy-l- E 9 i i gz f S e 8 butene was prepared by emulsion polymerization at 41 E2332: a 250 A 3: F. in accordance with the following rec pe: H Can-pounded 11/2 n 37 Pam by Weight Oven aged 24 hours at 212 F.: Butadiene 300%.m0 u pi 1770 2 phenyl 4 lauryloxyl-butene 2S Tenslle, P- 1770 water 155 Elongation, percent 300 Methanol .25 f Potassium fatty acid soap S RemhePwPercent Te pd d l mercaptan Q28 Abrasion loss, grams (35 minutes cure time) 2.73 Cumene hydroperoxide 0.101 The butadiene/ 2 phenyl-4-lauryloxy-l-butene copoly- 'FeSO .7H O 0.167 mer was also evaluated in a carcass recipe using the fol- K P O 0.198 lowing formulation: K01 0.50 Parts by weight Parts by weight Copolymer 100 Carbon black (Philblack O) Zinc oxide 3 Stearic acid 2 Flexamine 1 l Circo-Para 2 5 Sulfur 1.75 Santocure 3 0.95

A physical mixture containing percent of a complex cliarylamine-ketono reaction product and 35 percent of N,N- diphenyl-p-phenyleuediarnine.

A blend of equal parts of Circosol-ZXH with Parnflux Circosol-2XH: A petroleum hydrocarbon softener, containing hydrocarbons of high molecular weight, in the form of a heavy, viscous. transparent, pale green, odorless liquid of low volatility; specific gravity 0.940; Saybolt Universal viscosity at 100 F., about 2000 seconds. merized hydrocarbon.

a N-cyclohexyl-iZ-benzothiazolesulfenamide.

Paraflux: Saturated poly- Cop'olymer Carbon black (Philblack O) 25 Zinc oxide 3 Stearic acid 2 Agerite resin D l Paraflux 5 Staybelite resin 3 2.5 Sulfur 2.5 Santocure 2 0.95

1 Polymerized trimethyldihydroquinoline.

"As defined above.

8 Hydrogenated rosin.

Reaction product of butyraldehyde and butylidene aniline.

The compounded stocks were cured 30 minutes at 307 F. and physical properties determined. The following results were obtained:

Unaged samples:

Compression set, percent 13.0 300 modulus, p. s. i 820 Tensile, p. s. i 1000 Elongation, percent 320 200 F. maximum tensile, p. s. i 360 AT T. 27.4 Resilience, percent 78.1 Shore hardness 44 Compounded MS-1 /2 at 212 F 24 TRfreeze point, C 50 Oven a3ed-24hoursat212-F.: p

Tensile, p. s. i. 830 Elongation, percent. 260 AT F. 24.0 Resilience, percent 80.8 Shore hardness 48 Example XVI A butadiene/acrylouitrile/Z-phenyl-4-hydroxy-l-butene terpolymer was prepared by emulsion polymerization at 41 F. in accordance with the following recipe:

Parts by weight Butadiene 70 Acrylonitrile 10 2-phenyl-4-hydroxy-l-butene 20 Water 180 Potassium fatty acid sap.... 5 Tert-dodecyl me'rcaptan Q 0.2 Diisopropylbenzene hydroperoxide 0.086 eso,.71r,o 0.111 Kmo g 0,132 KC 0.5

Unaged samples:

Compression set, percent ...-'11.1 300% modulus, p. s. i 1975 Tensile, p. s. i 3640 Elongation, percent 495 200 F. maximum tensile, p. s. i 1970 Green tensile Good AT F 69.9 Resilience, percent 61.8 Abrasion loss, grams (35 minutes cure time) 3.09

' Extrusion at 250 F. in./min.- 35.2 Extrusion at 250 F. g./min 75.5 Compounded MS-1 /z 47 Oven aged 24 hours at 212 F;.: I

300% modulus, p. s. i 3360 Tensile, p. s. i 3580 Elongation, percent -2 320 ATg; F 56.8 Resilience, percent 66.4

Abrasion loss, grams (35 minutes cure time)-.. 2.93

The terp'olymer was also evaluated in a carcass recipe using the formulation given in Example XV except that 0.6 part Santocure was used instead of 0.95, part and 0.12 part A-32 was used instead of 0.19pa1t'. The compounded stocks were cured 30 minutes at 307, F. and physical properties determined. The following results were obtained:

Unaged samples:

18 Oven aged 24 hours at 212 F.: 3 1

300% modulus, p. s. i 1425 Tensile, p. s; i 2715 Elongation, percent --'430 AT F 32.1 Resilience, percent a 75.5 Shore hardness 5 56 Example X VII 2-phenyl-4- (N,N-dimethylaminoacetoxy)-1-butene, was prepared by the reaction of 2-phenyl-4-chloroacetoxy-1- butene and dimethylamine. Theproduct had the follow:- ing properties: v V

Boiling point, 130-133 C. at 1.4 mm. Hg; refractive index, 11 1.5210; density, r1 1.0306; molar refractivity, M 69.3; bromine number, 67. Analysis of the material gave a nitrogen content of 5.85 percent.

A copolymer of butadiene and 2-phenyl-4-(N,N di"- methylaminoacetoxy)-1-butene, was prepared by emulsion polymerization at 41 F. in accordance with the following recipe: t

' Parts by weight Butadiene 4---. 2 phenyl 4 (N,N-dimethylaminoace toxy)-1-butene 25 Water Methanol '25 Potassium fatty 'acid soap 5 Tert-dodecyl mercaptan 0.20 Diisopropylbenzene hydroperoxide 0.194 FeSO .7H O 0.278 K4P207 KCl 0.50

A conversion of 58 percent was reached in 21.1 hours;

The reaction was shortstopped with 0.20 part di-terther) was added as the antioxidant.

butylhydraquinone (based on monomers charged). Two

parts phenyl-beta-naphthylamine (based on parts rub- Coagulation was effected by the salt-alcohol method. The polymer had a Mooney value (ML-'4) of 40. I i

The butadiene/2-phenyl-4-dimethylaminoacetoxy-l-bu tene was compounded according to the'toll'owing'tread formula: I

Par'tsby weight Copolymer 100 Carbon black (Philblack O). 50 Zinc oxide 3 Stearic acid 2 Flexamiue 1 1 Circo-Para 5 Sulfur l 1.75 Santocure 1 -1 As in Example XV. I I

The compounded stocks were cured 30 minutes at 307 F. and physical properties determined. The following results were obtained: I Unaged samples:

Compression set, percent 13.1 300% modulus, p. s. i 1190 Tensile, p. s. i -2685 Elongation, percent..' {510 200 F. maximum tensile, p. s. i 1340 AT F 80.1 Resilience, percent.'. 59.3 Abrasion loss, grams (35 min. cure time) 5.39 Extrusion at 250 F., in./min 35.5 Extrusion at 250 F., g./min 77 Compounded MS-lVz 37 Oven aged 24 hours at 212 F.:

300% modulus, p. s. i 2230 Tensile, p. s. i 2865 Elongation, percent 370 AT F. 68.3 Resilience, percent 66.2

Abrasion loss, grams (35 min. cure time)-- 4.40

19 As many possible embodiments may be made of this invention without departing from the scope thereof, it is to be understood that all matter herein set forth is to be interpreted as illustrative and not in a limiting sense.

We claim: 1. As a new composition of matter, a copolymer of a compound of the formula where R is an aryl radical, A and B are selected from the group consisting of H, methyl and ethyl radicals, and X is selected from the group consisting of and --B. where R is selected fiom the group consisting of saturated aliphatic radicals, and substituted saturated aliphatic radicals; and

a -R, -("JR", (CH,GH,0).H

and

where R is selected from the group consisting of radicals having aliphatic unsaturation and n is an integer from 1 to 16 and a conjugated diene.

. 2. The composition of claim 1 in which said conjugated diene is butadiene.

3. A vulcanized polymer of claim 1 in which there is incorporated a reinforcing agent is selected from the group consisting of carbon black and silica.

4. The composition of claim 1 in which said conjugated diene is isoprene.

5. As a new composition of matter, a copolymer of 2-phenyl-4-acetoxy-l-butene and a conjugated diene.

v 6. As a new composition of matter, a copolymer of 2- phenyl-4-hydroxy-l-butene and a conjugated diene.

7. As a new composition of matter, a copolymer of 2-phenyl-4-acetoxy-1-butene and butadiene.

, 8. As a new composition of matter, a copolymer of 2-phenyl-4-hydroxy-l-butene and butadiene.

9. As a new composition of matter, a copolymer of 2-phenyl-4-acetoxy-l-butene and isoprene.

10. As a new composition of matter, a copolymer of 2-phenyl-4-lauryloxy-l-butene and butadiene.

11. As a new composition of matter, a terpolymer of 2-phenyl-4-acetoxy-l-butene, butadiene, and styrene.

12. As a new composition of matter, a terpolymer of Z-phenyl-4-hydroxy-l-butene, butadiene and styrene.

"13. As a new composition of matter, a copolymer of 2-phenyl-4-capryloxy-l-butene and butadiene.

14. As a new composition of matter, a copolymer of 2-phenyl-4-monochloroacetoxy-l-butene and butadiene.

15. A rubbery copolymer comprising 40 to 85 parts by weight of a conjugated diene and 60 to parts by weight of a compound of the formula 20 where R is an aryl radicaL'A 'andB are selectedfirom the group consisting of H, methyl and -'ethyl-" radicals, and X is selected from the group consisting of and i rated aliphatic radicals, and substituted saturated aliphatic radicals; and

where R" is selected from the group consisting of radicals having aliphatic unsaturation and n is an integer from 1 to 16. I v 16. A vulcanized polymer of claim 15 in which there is incorporated a reinforcing agent is selected from the group consisting of carbon black and silica.

17. In the method of preparing a copolymerby aqueous emulsion polymerization of a conjugated diene and a compound of the formula where R is'an' aryl radical, A and B are'sel'ected from the group consisting of H, methyl and ethyl radicals, and X is selected from the group consisting of --H, R and CR where R is selected from the group consisting of saturated aliphatic radicals, and substituted saturated aliphatic radicals; and p where R" is selected from the group consisting of radicals having aliphatic unsaturationand n is an integer from 1 to 16, the improvement which comprises adding a watersoluble diluent to said aqueous emulsion.

18. In the polymerization of butadiene and Z-phenyl- 4-lauryloxy-l-butene in aqueous emulsion, the improvement which comprises adding methanol as a watersoluble diluent to said emulsion.

19. In the polymerization of butadiene and Z-phen'yl- 4-(N,N-dimethylaminoacetoxy)-l-butene by emulsion polymerization, the improvement which comprises adding methanol as a watersoluble diluent to said emulsion.

References Cited in the file of this patent Price et al.: Jour. Am. Chem. Soc. 71 2860-2 (19 49). 

1. AS A NEW COMPOSITION OF MATTER, A COMPOLYMER OF A COMPOUND OF THE FORMULA 